Method of molding resin-bearing vegetable shell material



Patented May 4, 1948 METHOD OF MOLDING RESIN-BEARING VEGETABLE SHELL MATERIAL Edward Van der Pyl, Holden, Mass., assignor to Agicide Laboratories, Inc., Racine, Wis., a corporation of Delaware No Drawing. Original application November 16,

1938, Serial No. 240,792. Divided and this application April 7, 1943, Serial No. 482,219

3 Claims.

My invention relates to a method of forming molded articles and more particularly to the production of shaped articles made from resin bearing vegetable materials. The application is a division of my application Serial No. 240,792, filed November 16, 1938, and issued as Patent No. 2,319,182, May 11, 1943.

The principal object of the invention is to provide amethod of making shaped molded articles from vegetable materials comprising ingredients that are thermoplastic and capable of being softened and molded under heat and pressure.

I have discovered that vegetable shell materials, such as the shells of nuts, the endocarps of drupes, the barks of trees, the hulls of grains and seeds and the cones or strobiles of coniferous trees, comprise thermoplastic ingredients, and that they may be used as base substances which are moldable under heat and pressure either by themselves or with other thermoplastic materials, such as natural or synthetic or artificial resins or materials forming the same. These shell materials may also be employed with modifying agents which affect the hardness, strength, cohesion, wearability, resistance to abrasion and other physical properties of the molded product, or they may be employed as thermoplastic fillers or lmodifying agents with other moldable materia s.

I prefer to use those nut shells, fruit stones, barks, grain hulls, seed shells and like bodies which are thermoplastic to such an extent that they may be consolidated and molded without the aid of other thermoplastic materials and preferably by means of moderate pressure at a comparatively low temperature, such as 1 to tons pressure per square inch at 1 20 to 200 C. As examples of nut shells which are particularly serviceable, I may use those of the walnut, brazil nut, hickory nut, butter nut, pistachio nut, cocoanut, pecan nut, peanut, filbert nut, acorn and other nuts of like character. I may also use various other types of materials, which are herein considered as wood or vegetable shells, such as the coffee bean, which has preferably been roasted, the shell of the cacao bean from which chocolate is made, the endocarp or outer shell covering of the stones of drup'es or fruits, such as the apricot, peach, plum, olive, cherry and othersimilar fruits. Likewise, I may use as such vegetable shells the barks of trees, such as the poplar, oak, pine, elm, maple, birch, beech, alder and other trees and shrubs which are either deciduous or evergreen. Similarly, the hulls or outer coverings of various grains and seeds, such as wheat, oats, barley, rye and the like are sufii ciently thermoplastic so that they may be compressed under heat and pressure to form a useful solid body; and these are to be considered as wood or vegetable shells within the scope of my invention.

Various methods may be employed for molding or shaping articles from the wood shells, but this is preferably accomplished by means of heat and pressure applied directly to the raw material,

such heat and pressure being suflicient to cause the resinous ingredients of the vegetable: shellit is found that a temperature of 140 to 160 C.

or higher at pressures of from 1 to 20 tons per square inch will mold very satisfactory articles from the materials above listed. For example, walnut shells, after the meats have been removed, may be crushed to 100 grit size and then compressed in a steel mold in a power press which is heatedby steam. A pressure of5 tons per square inch and a temperature of about to C. for 10 minutes gives a molded article of a brown black color which has a density almost as high as the true density of the shell material. Similarly, the shells of pecans, filberts, brazil nuts and cacao beans may be molded to a very dense, strong and substantially non-porous body by being pressed for 10 minutes at 160 C. under a pressure of 10 tons per, square inch. The same general pressure and temperature conditions hold good for the stones of fruits, the barks of trees and the shucks or hulls of wheat, oats and other grains. Wide variations in the pressure may be made, depending on the nature of the material being molded; and the temperature may also be suitably adjusted to secure the best results, within the limits of the press and below that temperature at which the shell material is destructively aiiected.

The shell material looks and acts like a natural resin, to some extent, and it may be accordingly treated merely as a substance capable of being softened or plasticized under heat and pressure. Molded articles made of the nut shells as above described have a high strength and many'of the favorable characteristics of synthetic resins, For example, molded walnut shell, pressed under tons per square inch at about 160 0., was found to have a cross bending ruptural strength of 6000 pounds per square inch.

The resin-like shell material may also be- The-- addition of 1% or 2% by weight or more of a' synthetic resin, such as thepotentially reactive condensation product of phenol and formaldehyde, will aid in the molding operation. For. example, the pressure required toimold pulverized walnut shells at 160 C. may be-.20tons.to.

give a desired product; whereas the addition of 2% of a potentially reactive phenol formaldehyde resinoid in the liquid or powder form will make; it possible to obtain an equally satisfac- 4 is compatible with the vegetable shell material under the conditions of molding. As an example of the method of using such resins, the shell material may be wet with an equeous solution of urea formaldehyde and then driedprior to molding: Similarly, cellulose acetate is an agent which is capable of flowing on the surface of the shell material and aiding in cementing the grains together.

Asan: example, afinely comminuted nut shell material-maybe mixed with a lesser amount of urea-formaldehyderesin in aqueous solution, the mixture driedandthen subjected in a mold to a pressure of under three tons per square inch at a temperature between 120 and 180 C.

I may also: use various agents which act as plasticizers'orlubricants, in that they aid the molding of the shell material, Whether or not toryproduct'with a pressure as lowas 2 or 3 tons per-square inch. Strong and dense bodies may bemade. of walnut shells molded: with .l% or. moreof Canada balsam, rosin, shellacor other" material may constitute less than 50% of theproduct andthus act somewhat as a filler for the resin employed as the base substance.

When used as afiller, the vegetable shell distinguishes materially from standard fillers, such as Wood flour or sawdust used in the industry; is not thermoplastic since ordinary sawdust under the pressure and temperature conditions normally employed in the manufacture of the molded article; whereas the wood 'shell is thermoplastic and thus forms an integral union :with the material which it supplements or reinforces. That the thermoplastic shell material is capable of being shaped by heat and pressure so that it flows readily and unitesphysically with the-synthetic resin that is being employed;

Hence; the final product may be substantially non-porous and with the filler in a very intimatecontactwith the resin employed as the base substance.

Numerous types of synthetic resins which are well-known intheindustry may be used with the vegetable shell material; 1 Examples of these are -po lymerizable vinylcompounds, including vinyl chloride, vinyl I acetate and vinyl chloro-' acetate, andpolymerizable unsaturated methylene'compounds, such as the esters of acrylic acid on alpha substituted acrylic acid; of which methyl methacrylate is an example. Combinations of such vinyl resins may also be used, such as--methyl inethacrylate copolymerized with methacrylic acid. I may alsoemploy any potentiallyreactive fusible or heat settable resinoid; such as the condensation product of phenol and-formaldehyde reacted inthe presence'of ammonia,.or their homologues, or the phthalic glycerol-types of resins, or theurea resins,v or any othersuitable moldable composition; which;

other thermoplastic bodies are present. For ex ample, a small amount of water is found to lower the-pressure by or so for the production of a moldedbody of desiredcharacteristics. For example-i-from 8"to'-16% of water may be used With-the shell material for that purpose. Too much .water; however,-is not desirable since the article-may blister somewhatduepossibly to the presence of excess steam. This water may serve asa mechanical lubricant, or-as-a plasticizer, or its =beneficial effectmay possibly be due to some chemicalvtransformation. that takes place under the heat and pressure applied.

Various-other types of materials may be used as plasticizersw I have 'found that hexamethylenetetramine'in suitablaproportions, such as 5 to 10% or more-will serve as -a hardening agent and increasev the-strength of the molded shell material.- An.appreciable-hardening efiect is also obtained.-by using@2%-to 6% or moreoi aniline-or :of-iuriural in a' 40% formaldehyde solution. Numerous. other plasticizers and modi fying agents Wellknown in the resinoid art may beemployed-with-the wood shell-material. I have also observed--that 2.5%-to-7.5% of a20% aqueous solution of KOH' or: Na'OI-I' lowers the l pressurerequired for-molding 'a'body of given density; Numerous combinations of these different materials -may "be used andthe proportions of these modifying agentsmay-varywidely. It

is to be noted that only a small amount of phenol or furiural'formaldehyda-such -as'1% to*5% by weight, is. suflicient "to impart-a very high If :the :shel-limaterialcontains/too much of an oil which detrimentally affects the 'plasticizing or molding .operation, thisroil may-be removed priorto the molding? of. the :body. For example, cofiee may belroastedflto remove surplus oil, and the.

roasted productwill moldt to form a much stronger body than: does rthe -unroasted material. If, however, the =quantity'of-oi1 is not too great in a given shel-l'material; then it may be allowed to remain. -'Also,=- one may: moldtthe shell material with agents,- such as barium carbonate or barium sulfate, whieharecapable-of taking up theex trudedoil and'aiding inbinding the shellmaterial together. Cacao-shells give ofi oil in the mold .which may be initially removed by washing the:materiala-ivith hot Water. The: stones of fruits should'preferably be}washed--with-water to remove the surface-sugar which sees not aid in the plasticizing-operation.

The molded nut shells provide a body of higher elasticity than has the reacted phenol formaldehyde condensation product,-although it is not quite as hard. He'ncepthis characteristic makes itdesirable in some instances to combinethe stronger phenol formaldehyde resin with the moreelastic wood shell material. The various materials that arches-t molded with the wood shell are thoseofsimilar resin-like characteristics, although numerous other. ,substances may be incorporated with tnewooa shell material as fillers or inert bodies which provide strength, durability, abrasion resistance sorpother desired properties. i

The vegetable shell materialmay be employed as a bond for numerous types of granular grains of which crystalline alumina silicon carbide, boron carbide and diamonds are-examples. This shell material serves like a resin in its bonding properties. For example, a grinding wheel" or other abrasive article may be made by mixing suitable proportions of abrasivegrains andthe bond, such as 100 parts by-wight of abrasive grains with to 100 parts by weight of the shell material. These proportions may be more widely varied, if desired. This mixture of abrasive grains of suitable grit size and the shell material, preferably in a pulverized former in the same grit size as the abrasive grains, may be placedin a mold and heated and compressed as required, such as at a temperature of 160 to 200 C. and a pressure of 1 to tons per square inch. The wood shell material may also serve as a bond for numerous other commercially useful materials, such as asbestos, sand, cork, particles of wood and numerous other materials.

While the theories and the principles of chemistry and botany underlying the utility of such materials are not understood, it is believed that these wood or vegetable shells comprise cellulose, the pentosans and lignin in such proportions and of such character that a very considerable percentage of a thermoplastic ingredient is present. It is thought that the lignin and pentosans are particularly important for this purpose and are instrumental in imparting the desired properties to the crushed shell material. I have noted that a nut shell, such as walnut or pecan, when ground to a fine size and observed under the microscope, has a resin like appearance very much like a powdered synthetic resin formed as the condensation product of phenol and formaldehyde. This powdered shell material has a conchoidal fracture and is translucent or transparent. It is generally of a very light color but when molded it takes on a dark brown or black color.

In an article by Boswell found on page 971 of volume (1936) of the Biochemical Journal, the analysis of brazil nut shell was given as follows:

Per cent Benzene-soluble 4.69 Alcohol-soluble 1.06 Water-soluble 1.64 5% NaOI-I (cold)-soluble 16.00 Lignin 53.25 Cellulose "25.47

The cellulose fraction was found to give a high yield of furfuraldehyde, and the pentosan content of the cellulose was given as 29.3%. Bos- In volume 60 v(1938), page 1506 of the Journal of the American Chemical .Society, Ramanathan gives the following analysis ofcocoanut shells which have been dried at C. with a moisture loss 8.78%2, i

- l 1 7 Per cent Cold watersoluble 0.19 Hot water soluble 3.51 Alcohol water soluble 2.51 Benzene soluble 0.27 1% alkali soluble 18.8 Ash (mostly K2003) 0.6'1 Lignin 36.51 Cellulose 53.06 Total pentosans. 29.27 Pentosans in the cellulose 20.54

Pentosans form 38.69% of total cellulose.

Similarly, I havefound that the walnut shell analyzes as follows:

Per cent Specific gravity 1.417 Pentosan and lignin content 63 Cellulose, not over 37 Ordinary wood has about 20 to 30% of lignin and pentosan; hence it will be noted that the shells have a very high content of lignin and the pentosans, in comparison with the wood derived from the interior .of the tree and not the bark. I have found that maple wood sawdust is not suifioiently thermoplastic to permit it to be compressed into a hard coherent body at a temperature of 160 C. and a pressure of 20 tons per square inch. On the other hand, powdered walnut shell may be compressed into a dense mass of 1.40 specific gravity (true density=1.41'7) by a pressure of 5 tons per square inch at a temperature of about to C.

While I have attempted to explain some of the theories underlying this invention, yet the claims are not to be construed as dependent thereon. Also, the examples given are to be considered as illustrating the invention and not as limitations thereon, except as set forth in the claims appended hereto. The term vegetable shell. material and similar expressions are to be interpreted as including all of the classes of substances above defined, and particularly the shells of nuts, tree barks, fruit stone shells, grain hulls, seed shells and equivalent resin-like materials.

I claim:

1. The method of producing molded products from resin bearing vegetable shell material having a lignin and pentosan content of more than 50% by weight, which comprises finely grinding said shell material to expose a large area thereof, introducing the resulting ground material in substantially dry form into a mold and subjecting all of the ground material after its introductioirithermoplasticiingredientszofiieachr panticleeto :fiew

and unite with the lignin and pentosan thermor plastic-ingredients of other particles throughout the mold ,to. form .dense, relatively a-inela-stic coherenteunitary.productsof substantially-uniformproperties throughout.

.2. Thenmethodgof, pro in d: uc irom resinebearin uvegetable shell material zhavingraelignin and pentosancontent of moreathan 50 by. weight, which comprises finely grinding said shellgmaterial to a fine particle size,,-.introdu'cingthe resulting. ground materia1,-and.a.-mold-. able resin into a mold and subjecting all of the ground-mat'erial'in substantiallydry form to heat betWeen-IZO and 200 -C.- and pressure between one-and twenty tons per squareinch to cause-the ligni-n and pentosan thermoplastic ingredients of each particle to flow and unite with thezmoldable resin-and with the lignin and pentosan thermoplastic ingredients of other particles throughout t-heimate-rial-inthe mold to form dense; relatively inelastic; coherent, unitary products of substantially uniform properties throughout.

2'3; -The-method of producingmolded-products from resin bearing- -nut shell -material having a lignirrand pentosancontent ofmore than 50% by gweight; which comprises finely comminuting said? nutshell-material to expose a large area thereof in-troducing the resultant ground material intoamold with alesser amount'of a potentially reactive, heatusettable, urea-formaldehyde resin in aqueous solution, drying the resulting zncrennucesgolmnf 1 The following:zrefenencesearea :of' record in ethe fileof thiszipatentr V UNITED fiTATEsrPATEN sjj" I'Eat'e;

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